Fuel detergents

ABSTRACT

The reaction products of hydrocarbon polyamines having a long, substantially aliphatic, hydrocarbon chain bonded to a di- or higher polyamine with certain polyfunctional coupling agents find use as detergents in distillate fuel compositions. The hydrocarbon group is normally branched chain and derived from natural sources or polyolefins, substantially free of aromatic substitution and of about 420 to 10,000 molecular weight. The poly-functional coupling agents are certain polyhalides, polycarboxylic acids, and organic polyisocyanates.

llnited States Patent [191 Honnen et al.

[ 1 Jan. 15, 11974 FUEL DETERGENTS [73] Assignee: Chevron ResearchCompany, San

Francisco, Calif.

[22] Filed: May 24, 1972 [21] Appl. No.: 256,289

[52] US. Cl 44/66, 44/71, 44/72, 44/63, 252/50, 260/453 AR, 260/453 AL[51] Int. Cl C101 1/22 [58] Field of Search 44/66, 71, 72, 62, 44/63;252/50; 260/404.5, 583 P, 561 R, 453 AR, 453 AL [56] References CitedUNITED STATES PATENTS 3,600,413 8/l97l Grimm 44/72 om) et a] 44/72Annable et a1. 44/66 Primary Examiner-Daniel E. Wyman AssistantExaminerY. H. Smith At't0meyJ. A. Buchanan, Jr. et a].

[57] ABSTRACT The reaction products of hydrocarbon polyamines having along, substantially aliphatic, hydrocarbon chain bonded to a dior higherpolyamine with certain polyfunctional coupling agents find use asdetergents in distillate fuel compositions. The hydrocarbon group isnormally branched chain and derived from natural sources or polyolefins,substantially free of aromatic substitution and of about 420 to 10,000molecular weight. The poly-functional coupling agents are certainpolyhalides, polycarboxylic acids, and organic polyisocyanates.

16 Claims, N0 Drawings FUEL DETERGENT? BACKGROUND OF THE INVENTION 1.Field of the Invention Deposits tend to build up in the carburetorthrottle body and fuel-intake systems of modern internal combustionengines. The problem becomes critical in automobiles that frequentlyoperate under idling conditions in heavytraffic, such as taxi fleets,delivery fleets, and the like. However, these deposits can be found inheavy amounts in virtually all services, including normal passenger carservice. Common results of intake system deposits are carburetormalfunction, poor intake valve seating, heavy manifold deposits andrestricted breathing. Detergents are included in distilate fuels tomaintain carburetor cleanliness and to exert an extended detergentaction over the entire intake system. It is extremely difficult toobtain a satisfactory detergent which is effective in the various areasand under the different conditions in which deposits occur in theinternal combustion engine. These problems are made more difficult tosolve by the low concentrations in which detergents are used in fuels.

2. Description of the Prior Art Several recent patents have disclosedthe usefulness of high molecular weight hydrocarbyl polyamines aseffective detergent/dispersa'nts in lubricating oil compositions andfuels, US. Pat. Nos. 3,438,757; 3,574,576; and 3,565,804.

SUMMARY OF THE INVENTION The complex reaction products of certain highmolecular weight branched chain, aliphatic N-hydrocarbyl alkylenepolyamines with selected coupling agents which are polyfunctional lowmolecular weight carboxylic acids, acid halides, anhydrides,polyisocyanates, or hydrocarbon polyhalides can function as detergentsin hydrocarbonaceous liquid fuels for internal combustion engines. Thehydrocarbyl polyamine reactants have'molecular weights in the range ofabout 450 to 10,000. The hydrocarbyl radical will normally be de-DETAILED DESCRIPTION OF THE INVENTION The compositions of this inventionare the complex reaction products of certain high molecular weightbranched chain,-aliphatic N-hydrocarbyl alkylene polyamines withselected coupling agents which are polyfunctional low molecular weightcarboxylic acids, acid halides, anhydrides, isocyanates orhydrocarbylhalides. Of course, the products of the coupling reactionsare normally of higher average molecular weight than the hydrocarbylpolyamine reactants and normally consist of the condensation product oftwo hydrocarbyl polyamines through the coupling agent by reaction at aprimary or secondary amino nitrogen of the polyamine. Considering thecomplexity of the polyamine reactants themselves, the several possiblesites of reaction therein, and the possibility of coupling two, three ormore polyamines, it is difficult to obtain a practical gen, which may bealiphatic, alicyclic, or aromatic, or

combinations thereof, e.g., aralkyl. Preferably, the hydrocarbyl groupswill be relatively rree of aliphatic unsaturation, i.e., ethylenic andacetylenic, particularly acetylenic. The hydrocarbyl polyamines willhave average molecular weights in the range of about 450 to 10,000, moreusually in the range of about 750 to about 6,000. When the hydrocarbylgroups are of lower molecular weight, the average number of hydrocarbylsubstitutes in the polyamine can be greater than one. The

hydrocarbyl will normally be aliphatic, having from zero to two sites ofunsaturation; more usually zero to two sites of ethylenic unsaturationand preferably from zero to one site of ethylenic unsaturation.

The hydrocarbyl group willnormally be derived from a polyolefin derivedfrom olefins of from two to six carbon atoms (ethylene beingcopolymerized with an olefin of at least three carbon atoms), or from ahigh molecular weight petroleum-derived hydrocarbon.

For the most part, the polyamines used in this invention will be of thefollowing general formula:

. wherein:

U is alkylene of from two to six carbon atoms, more usually of from twoto three carbon atoms, there being at least two carbon atoms between thenitrogen atoms;

a is an integer of from 0 to 10, usually of from 1 to 6, and moreusually of from 1 to 4;

b is an integer of from 0 to l and preferably 0;

a+2b is an integer of from 1 to 10, more usually an integer of from l to6 and preferably an integer of from 1 to 4;

c is an integer or fractional number (when averaged over the entirecomposition) in the range of from I to .5, preferably l to 3, and equalto or less than the number of nitrogen atoms in the molecule, usually onthe average less than the total number of nitrogen atoms in themolecule;

R is an aliphatic or alicyclic branched hydrocarbyl radical derived frompetroleum hydrocarbons or olefin monomers of from two to eight carbonatoms, preferably of from three to four carbon atoms, ethylene beingcopolymerized with a higher homolog (an olefin of at least three carbonatoms) and having from zero to two sites of aliphatic unsaturation, moreusually from zero to two sites of ethylenic unsaturation and preferablyfrom zero to one site of ethylenic unsaturation, having greater than 30carbon atoms and not more than 300 carbon atoms, more usually 50 to 200carbon atoms and preferably 60 to 200 carbon atoms;

A is hydrogen, hydrocarbyl from one to carbon atoms orhydroxyhydrocarbyl of from one to 10 carbon atoms,

X is hydrogen, hydrocarbyl of from one to 10 carbon atoms orhydroxyhydrocarbyl of from one to l0 carbon atoms and may be takentogether with A and the hydrogen to which A and X are attached to form aring of from five to six annular members having from zero to one oxygenannular members, one nitrogen annular member, and from four to fivecarbon annular members,

x is an integer of from 0 to l,

y is an integer of from 0 to l, and

x+y is equal to l.

The alkylene radical, indicated as U, will have from two to six carbonatoms, the nitrogens connected by U being separated by at least twocarbon atoms. The alkylene group may be straight chain or branchedchain, the remaining valences of the alkylene group being on differentcarbon atoms. Illustrative alkylene groups include ethylene,trimethylene, tetramethylene, pentamethylene, hexamethylene,1,2-propylene, Z-methyll,3-propylene, l,4-(2,3-dimethylbutylene), etc.

The hydrocarbyl radical indicated by R may be aliphatic or alicyclicand, except for adventitious amounts of aromatic structure present inpetroleum mineral oils, will be free of aromatic unsaturation. Thehydrocarbon groups are derived from petroleum mineral oil orpolyolefins, either homo-polymers or higher order polymers, of l-olefinsof from two to six carbon atoms, ethylene being polymerized with ahigher homolog. The olefins may be monoor poly-unsaturated, but thepoly-unsaturated olefins require that the final product be reduced toremove substantially all of the residual unsaturation.

Illustrative sources for the high molecular weight bydrocarbons frompetroleum mineral oils are naphthenic bright stocks. For the polyolefin,illustrative polymers include polypropylene, polyisobutylene,poly-l-butene, copolymer of ethylene and isobutylene, copolymer ofpropylene and isobutylene, poly-l-pentene, poly-4-methyl-l-pentene,poly-l-hexene, poly-3- methylbutene-l etc. I

The hydrocarbyl group will normally have at least one branch per sixcarbon atoms along the chain, preferably at least one branch per fourcarbon atoms along the chain, and particularly preferred that there befrom 0.5 to one branch per carbon atom along the chain (at least onebranch per two carbon atoms along the chain). These branched chainhydrocarbyl groups are readily prepared by the polymerization of olefinsof from three to six carbon atoms and preferably from olefins of fromthree to six carbon atoms. The addition polymerizable olefins employedare normally l-olefins. The branch will be from one to four carbonatoms, more usually of from one to two carbon atoms and preferablymethyl.

The hydrocarbyl-substituted polyamine can be a polyethylene polyamine,or polypropylene polyamine, where, for example, the polyethylenepolyamine is of the general formula:

l-lb (-CH CHzAI-J .ilR siHuni-ni wherein:

a is in the range from I to 5;

c is in the range from I to 4 and equal to or less than the number ofnitrogen atoms; and

R is a branched chain aliphatic hydrocarbyl group derived from olefinsof from two to six carbon atoms and of average molecular weight in therange from about 420 to about 2,000, with the proviso that when themonomer is ethylene it is copolymerized with a higher homolog.

In order to include possible variations, the generic formula does notindicate to which nitrogen atom the R group and the H atoms are bonded.Rather, free valences are indicated by bars, and the total number of Rgroups and H atoms indicated next to the basic polyamine structure. Thegeneric formula employed provides a simple means for including thepossible variations that will occur when a polyamine is used havingnon-equivalent amine nitrogens. Numerous examples and illustrativecompounds within the above formula are given in US. Pat. Nos. 3,438,757and 3,574,576 which are incorporated herein by reference.

In preparing the hydrocarbyl-substituted polyamine reactants, rarelywill a single compound be employed. With both the polymers and thepetroleum-derived hydrocarbyl groups, the composition is a mixture ofmaterials having various structures and molecular weights. Therefore, inreferring to molecular weight, average molecular weights are intended.Furthermore, when speaking of a particular hydrocarbyl group, it isintended that the group include the mixture that is normally containedwith materials which are commercially available; that is,polyisobutylene is known to have a range of molecular weights, and mayalso include very small amounts of very high molecular weight materials.Furthermore, depending on the method of preparation, the end group ofthe polymer'may vary and may be terminated not only with an isobutenegroup, but with a lor 2- butene group.

Similarly, the alkylene polyamines which are commercially available arefrequently mixtures of various alkylene polyamines having one or twospecies dominating. Thus, in commercially available tetraethylenepentamine, there will also be small amounts of pentaethylene hexamineand triethylene tetramine. In referring to tetraethylene pentamine, forexample, it is intended not only to include the pure compound, but thosemixtures which are obtained with commercially available alkylenepolyamines. Finally, as indicated, in preparing the compounds of thisinvention, where the various nitrogen atoms of the alkylene polyamineare not equivalent, the product will be a mixture of the variouspossible isomers, and the coupling of the hydrocarbyl-substitutedpolyamines can produce a variety of possible final structures.

Coupling Agents The coupling agents which function to yield detergentsof the present invention upon reaction with the high molecular weighthydrocarbyl-substituted polyamines are normally telechelic (terminallyreactive) polyfunctional molecules of relatively low molecular weight.They may be classified among several general groups ofpolyfunctionalities. These functionalities are chemical groupingsdistinguished by their ability to react with primary or secondary aminonitrogen atoms in a hydrocarbyl-substituted amine to yield products inwhich the coupling agent is bound to said amino nitrogen by a chemicalbond.

liirne rTzation aTso alters the chemical nature of the amino nitrogen.The product of the reaction of polybutene ethylene diamine with l,4-dichloro-2-butene is expected to have properties which differ from that ofpolybutene ethylene diamine, in that all the amino nitrogens are allylicinstead of only one in the starting polybutene ethylene diamine.Similarly, the use of p-bis(chloromethyl)benzene as the coupling agentgives a product containing both benzylic and allylic amines. On theother hand, the use of acid halides, or acid anhydrides, converts theamines into amides with lower total bacisity as well as higher molecularweight.

1. Polycarboxylic acids, acid halides, anhydrides, or equivalents, whichreact with primary or secondary amino nitrogen to yield amides andpolyamides, or react with primary amino nitrogen to form imides, aresatisfactory coupling agents in the present invention. Examples of suchpolycarboxylic acids include oxalic, malonic, succinic, glutaric,adipic, pimelic, azelaic, sebacic and other a,w-dibasic acids ofrelatively low molecular weight and the hydrocarbyl-substituted acids ofthe same name. Unsaturated polycarboxylic acids such as maleic, fumaric,itaconic are useful coupling agents, as are the substitutedpolycarboxylic acids such as tartronic, malic, tartaric, nitriletriacetic, and citric acids. Coupling agents include aromatic carboxylicacids and equivalents such as phthalic anhydride, terephthaloylchloride, and preferably, pyromellitic dianhydride. In general, thepolycarboxylic coupling agents will be characterized by molecularweights below about 300 and carbon numbers in the range from C to aboutC 2. Organic polyisocyanates, such as toluene diisocyanate (made from2,1-amino toluene), react with primary or secondary amino nitrogen toyield hydrocarbyl-ureas or polyureas which are satisfactory fueldetergents. Examples of such organic polyisocyanates include phenylenediisocyanate, toluene diisocyanate, methylenediphenyldiisocyanate,alkylates methylenephenyldiisocyanate, hexamethylenediisocyanate, andpolymeric isocyanates, such as polymethylenepolyphenylisocyanate. Ingeneral, the organic polyisocyanate coupling agents will becharacterized by molecular weights below about 400 and carbon numbers inthe range from about 8 to about 20.

of this invention are low molecular weight telechelic preferred couplingagent of the invention because of their effectiveness in depositcontrol. Method of Preparation The coupling agents are illustrated bythe known, comercially available, chemicals previously discussed. Themethod of preparation of the hydrocarbylpolyamines has been describedand illustrated with numerous examples in U.S. Pat. Nos. 3,565,804,3,574,576 and 3,438,757 which are herein incorporated by reference. Theproducts of this invention are prepared by reacting a coupling agentwith a hydrocarbyl polyamine by directly mixing the reactants, orsolublizing in a mutual solvent such as benzene, xylene, or hexane. Ingeneral, the mole ratio of the reactants can range from 1:3

to 3:1. Normally, the reactions proceed by contacting the reagents, withstirring, at temperatures from about 25C. to about 200C. for from 1 to48 hours. The organic product is usually washed, the aqueous phaseremoved, and the product is stripped of solvent. Infra-red spectra weretaken routinely to check the product. Molecular weight measurementsindicate the products correspond to the coupling of two hydrocarbylpolyamines. To illustrate, the products obtained in the followingexamples were largely dimeric as shown by molecular weightdeterminations.

EXAMPLE I: Polyisobutenyl ethylene diamine (500 g., 0.281 mole) whereinthe polybutenyl is of average molecular weight 1,400, was heated to 115C. and 1,4-

= dichlor0-2-butene (21.9 g., 0.175 mole) was added in one step. Thetemperature was increased to 190C. for

20 minutes, then lowered to 150C. and held for 3.5 hours. Thetemperature was then increased to 210C. over a 35-minute period. Themixture was cooled, diluted with 1 liter of mixed hex anes, 800 ml. ofmetha- 'nol and 500 ml. of dilute NaOH. The resulting mixture was heatedto boiling and poured into a separatory funnel. The aqueous layer wasremoved and the organic layer was washed with 500 ml. of boiling water.The mixture was concentrated by distillation with final strippingcarried out on the solvent stripper at 100C for 1.5 hours to obtain 456g. of dimerized material dihalides, such as 1,4-dichloro-2-butene, orp-bis- (chloromethyl)benzene, generally c c in which the halogens areattached to different carbon atoms and preferably are separated byseveral carbon atoms. The organic dihalides react with primary orsecondary amino nitrogen to yield higher order amines. They are with thefollowing analysis molecular weight, 2,530: percent nitrogen, 1.34.

EXAMPLE II: Polyisobutenyl tetraethylene pentamine (464 g., 0.33 mol)wherein the polybutenyl is of average molecular weight 950 was heated toC, followed by the one-step addition of 20.4 (0.163 mol) ofl,4-dichloro-2-butene. The temperature was increased to C and held for 1hour and 20 minutes. Upon cooling, 600 ml. of mixed hexanes, 600 ml. ofisopropyl alcohol, and 300 ml. of water containing 15 g. of NaOI-I wasadded. The aqueous layer was removed and ml. more water added, followedby shaking. The aqueous layer was removed. Final washing was carried outwith 300 ml. of water. The organic layer was concentrated bydistillation, with final stripping to yield 465 g. of dimer: molecularweight 2,550: per cent nitrogen 4.33.

EXAMPLE III: Polyisobutenyl ethylene diamine of Example I (100 g., 0.056mol) was heated to 120C. p-bis(chloromethyl)benzene was added in onestep and the temperature increased to C and held for 3 hours 15 minutes.The mixture was diluted with hexane and isopropyl alcohol, washed withdilute NaOH and water, and stripped to yield 95 g. of dimer: molecularweight 2,700rper cent nitrogen 1.48 1R 1, 680 cm.

EXAMPLE 1V: Polyisobutenyl amine (206 g., 0.225 mol), wherein thepolyisobutenyl amine is of average molecular weight 820, was heated to110C and 1,4-

dich1oro-2-butene (12.8 g., 0.133 mol) was added in one step. Themixture was heated for about 7 hours with the temperature rising to133C. The mixture was cooled, diluted with mixed hexanes, washed withdilute sodium hydroxide, then washed with water until washings wereneutral. Solvent was removed from the mixture by stripping on thesolvent stripper at 100C for several hours to give 183.2 g. partiallydimerized material having the following analysis: molecular weight,1,290; percent nitrogen, 1.48.

EXAMPLE V: 25 ml. of pyridine and the polyisobutenyl ethylene diamine ofExample 1 (100 g.) were dissolved in 50 ml. of benzene and heated toreflux. Pyromellitic dianhydride (6.1 g., 0.028 mol) and 40 ml. of hotpyridine were added drop-wise over a 10-minute period. A completelyhomogeneous solution resulted. Heating at reflux was continued for 1hour minutes, then solvent was removed by distillation until thetemperature reached 180C. The mixture was cooled to 150C and held for 3hours, then cooled to room temperature and 100 ml. of toluene and ml. ofn-butanol were-added. The mixture was washed three times in 100 ml.portions of water containing 5 percent nbutanol, then concentrated bydistillation with final stripping yielding 99 g. of product; molecularweight 3,550; per cent nitrogen 1.54; IR, 1,635 cm (amide), and 1,725 cm(imide); base number of product, 19 mg. KOH/g; base number of startingmaterial, 53 mg. KOH/g; acid number of product, 6.1 mg. KOH/g. EXAMPLEV1: Terephthaloyl chloride (5.7 g., 0.028 mol) and the polyisobutenylethylene diamine of Example 1 (100 g.) were dissolved in 100 ml. ofbenzene and heated to reflux for 20 minutes. Solvent was removed atdistillation until the temperature reached 150C. This temperature washeld for 3.5 hours, followed by workup as in Example 111 giving 94 g. ofmaterial: molecular weight 3,380; percent nitrogen 1.53; IR 3,320 cm(NH), 1,650 cm (amide); base number of starting material 53 mg. KOH/g;base number of product 23 mg. KOH/g; acid number of product 1.8 mg.KOH/g. EXAMPLE V11: Polyisobutenyl ethylene diamine of Example 1 (672g.) was added to 150 ml. of toluene and 86.4 g. of diphenolicacid-dissolved in 300 m1. of tetrahydrofuran. The mixture was stirred at151C for 12 hours under nitrogen. The product was stripped to 325F andweighed 753 g.

EXAMPLE V111: 19.2 g. of trimellitic anhydride was mixed with thepolyisobutenyl ethylene diamine of Example 1 (672 g.) in 125 ml. oftetrahydrofuran. The mixture was stirred for 12 hours at about 163Cunder nitrogen. The product was stripped to 335F and weighed 696 g.

EXAMPLE 1X: Oleyl amine (52.6 g., 0.196 mol) in 150 ml. of xylene washeated to 100C and 1,4- dichloro-2-butene (11.1 g., 0.098 mol) was addedin one step. Heating was continued for 2% hours at which time thetemperature had increased to 141C. The mixture was cooled, washed withdilute sodium hydroxide, then washed with water until the washings wereneutral. The mixture was stripped on the solvent stripper to give 46.5g. of material having the following analysis: molecular weight, 700;percent nitrogen, 4.48; percent chlorine, 1.64.

EXAMPLE X: Ethylene diamine tetraacetic acid (29.2 g.) was mixed withthe polyisobutenyl ethylene diamine of Example I (896 g.) and 100 ml. oftoluene. The mixture was stirred at 325335F for 6 hours under a nitrogenatmosphere. About 6-7 cc. of H 0 was collected in a Stark trap and theproduct was stripped of toluene under reduced pressure.

EXAMPLE X1: N,N-bis-(2-hydroxyethyl)glycine (81.5 g.) was mixed withpolyisobutenyl ethylene diamine of Example 1 (1,010 g.) in 150 cc. oftoluene. The reaction mixture was stirred at 325330F. for 8 hours. Themixture was dissolved in hexane and filtered. The hexane was strippedoff under reduced pressure. EXAMPLE X11: ltaconic acid (26 g.) was mixedwith polyisobutenyl ethylene diamine (808 g.) and 150 cc. of toluene.The mixture was stirred at 325335F for 12 hours under nitrogenatmosphere. The toluene was removed under reduced pressure.

EXAMPLE X111: Polyepoxide (25 g.) was mixed with polyisobutenyl ethylenediamine of Example I (308 g.). The mixture was stirred at 280290F for 8hours under a nitrogen atmosphere. The finalproduct was stripped to250F.

EXAMPLE XIV: Epichlorohydrin (28 g.) was mixed with polyisobutenylethylene diamine of Example 1 (672 g.) and the mixture was stirred at230235F for 15 hours. The mixture was stripped to 325F under vacuum.

EXAMPLE XV: Polyisobutenyl ethylene diamine of Example I (900 g.) wasmixed with 900 g. of a neutral oil and stirred at 200F for 15 minutes.43.5 g. of toluene 2,4-diisocyanate was then added and the mixturestirred at 295-320F for 8 hours. The product was stripped, dissolved inhexane and filtered. The hexane was removed under reduced pressure.

EXAMPLE XVI: Fumaric acid (7.78 g.) was mixed with an approximatelyequimolar amount of the polyisobutenyl ethylene diamine of Example 1(100 g.) in 600 ml. of xylene. N was flushed during the reaction whichoccurred at xylene reflux temperature for 6 hours. 1.2 m1. of water wascollected overhead. 500 ml. of methyl alcohol and 100 m1. of H 0 wereadded to the reaction product and the polymer layer separated from theaqueous layer. The hexane solubles were azeotroped with benzene toremove excess water and the solvents were stripped under vacuum.Molecular weight about 2,380; percent nitrogen 1.37. EXAMPLE XVII:Maleic anhydride (5.4 g.) was mixed with 100 g. of the polyisobutenylethylene diamine of Example 1 in 600 ml. of xylene. The reaction mixturewas flushed with N and reaction occurred at the xylene refluxtemperature for 6 hours. About 1 ml. of water was collected as areaction product. The product was separated with ethanol-water severaltimes, azeotroped with benzene and stripped under vacuum. Molecularweight about 2,997; percent 1.33. EXAMPLE XVIII: d-tartaric acid (20 g.)was mixed with 100 g. of the polyisobutenyl ethylene diamine of Example1 in 600 ml. of xylene. The system was flushed with nitrogen and reactedat xylene reflux temperature for 6 hours. About 5.9 m1. of water wascollected as a reaction product. The polymer product was separated byadding about 500 ml. of ethanol percent) and m1. of water, boiling themixture, and removing the non-aqueous layer. This was repeated. Thepolymer product was then azeotroped with benzene to remove the lasttraces of water and the product was stripped 9 under vacuum. Molecularweight about 2,980; percent nitrogen 1.34. Compositions Depending on theparticular application of the composition of this invention, thereaction may be carried out in the medium in which it will ultimatelyfind use and be formed in concentrations which provide a concentrate ofthe detergent composition. Thus, the final mixture may be in a form tobe used directly upon dilution in fuels. The detergent will generally beemployed in a hydrocarbon base liquid fuel. The detergent may beformulated as a concentrate, using a suitable hydrocarbon solvent. Preferably,'an aromatic hydrocarbon solvent is used, such as benzene,toluene, xylene or higher boiling aromatics of aromatic thinners.Aliphatic alcohols of about three to eight carbon atoms, such asisopropanol, isobutanol, n-butanol and the like, in combination withhydrocarbon solvents are also suitable for use with the detergentadditive.

in the fuel, the concentration of the detergent will generally be atleast 100 ppm. and usually not more than 4,000 p.p.m., more usually inthe range of from about 200 to about 800 p.p.m; 1n concentrates, thedetergent will generally be from 1 to,50 weight percent, more usuallyfrom about 5 to 30 weight percent, and will generally not exceed 80percent by weight.

In gasoline fuels, other fuel additives may also be included such asanti-knock agents, e.g. tetramethyl lead, tetraethyl lead. Also includedmay be lead scavengers such as aryl halides, e.g. dichlorobenzene oralkyl halides, e.g. ethylene dibromide. A non-volatile lubricatingmineral oil, e.g. petroleum spray oil, particularly a refined naphtheniclubricating oil having a viscosity at 100F. of 1,000 to 2,000 SUS, is asuitable additive for the gasoline compositions used with the detergentsof this invention and its use is preferred. Similar hydrocarbon oils,such as polypropylene oils can also be used. These oils are believed toact as a carrier for the detergent and assist in removing and preventingdeposits. They are employed in amounts of from about 0.05 to 0.5 percentby volume, based on the final gasoline composition. Evaluation Todemonstrate the effectiveness of the compositions of this invention asdetergents, a number of fuel compositions were tested in asingle-cylinder engine having a compression ratio of 9:1, a bore of 3.25inches, a stroke of 4.5 inches and the displacement of. 37.22 cubicinches. To the fuel were added 1,000 p.p.m. of a carrier oil (naphthenicoil of 1,740 SUS at 100F.) containing sufficient detergent to give aconcentration of 250 p.p.m. detergent in the fuel. The duration of thetest was 12 hours, at 1,800 rpm, a jacket temperature of 212F, andengine manifold vacuum of -inch Hg, intake temperature of 95F, air/fuelratio of 14 and ignition spark timing 15 BTC. After the test, the enginewas disassembled and the deposits on the intake valve were weighed afterwashing with hexane. The results were as follows.

TABLE ll Hexane Washed Valve Deposits in e Composition Coupling AgentTABLE ll-Continued Composition Coupling Agent I Hexane Washed ValveDeposits in In Table 11 the roman numeral compositions refer to 1 theexamples previously given. The reference fuel contains 1,000 p.p.m. ofcarrier oil. The data graphically demonstrate the applicability of thecompositions of this invention. Excellent detergent and dispersantresults are obtained, which in most ca'ses are superior to thoseobtained from well-known and widely used dispersant/detergent additives.[t can be seen that the dimerized structures made from fairly lowmolecular weight amines, e.g. oleylamine, Example 1X, have very poorintake valve performance, while the higher molecular weight polybutenylamine products of Examples 1, ll and 1V, with the same coupling agent,give a very small amount of deposit. 4

The additives of this invention are able to function in both lubricatingoils and fuels. Moreover, they are readily available by simple syntheticmethods and they provide detergency without producing ash.

As will be evident to those skilled in the art, various modifications ofthis invention can be made or followed in the light of the foregoingdisclosure and discussion, without departing from the spirit or scope ofthe disclosure of from the scope of the following claims.

We claim:

1. A composition which is the reaction product of ahydrocarbyl-substituted polyamine wherein the hydrocarbyl is of from 40to 300 carbon atoms and is an aliphatic or alicyclic branched chainhydrocarbyl radical derived from petroleum hydrocarbons or polyolefinsof monomers from two to six carbon atoms, with the pro viso that whenthe monomer is ethylene it is copolymerized with a higher homolog; and acoupling agent selected from the group consisting of C C polycarboxylicacids, C -C polyisocyanates having a molecular weight below 400 and C Chydrocarbyl dihalides. i

2. A composition according to claim 1, wherein the hydrocarbyl polyamineis of the general formula:

a is in the range of 1 to 5;

c is in the range of 1 to 4 and equal to or less than the number ofnitrogen atoms; and

R is a branched chain aliphatic hydrocarbyl group derived from olefinsof from three to four carbon atoms and of an average molecular weight inthe range from about 560 to about 2,000.

3. A composition according to claim 2, wherein the hydrocarbyl polyamineis a polyisobutenyl ethylene diamine having from one to twopolyisobutenyl groups of from about 560 to about 2,000 average molecularweight.

4. A composition according to claim 2, wherein the hydrocarbyl polyamineis a polyisobutenyl diethylenetriamine having from one to twopolyisobutenyl groups of from about 560 to about 2,000 average molecularweight.

5. A composition according to claim 2, wherein the hydrocarbyl polyamineis a polyisobutenyl triethylenetetramine having from one to threepolyisobutenyl groups of from about 560 to about 2,000 average molecularweight.

6. A composition according to claim 2, wherein the hydrocarbyl polyamineis a polyisobutenyl tetraethylenepentamine having from 1 to 3 isobutenylgroups of from about 560 to about 2,000 average molecular weight.

7. A fuel composition having a major amount of a hydrocarbonaceousliquid fuel and in an amount to provide detergency, the reaction productof a hydrocarbyl amine wherein the hydrocarbyl is of from 40 to 300carbon atoms and is an aliphatic or alicyclic branched chain hydrocarbylradical derived from petroleum hydrocarbons or polyolefins of monomersfrom two to six carbon atoms, with the proviso that when the monomer isethylene, it is copolymerized with a higher homolog; and a couplingagent selected from the group consisting of C.,--C polycarboxylic acids,C -C polyisocyanates having a molecular weight below 400 and C Chydrocarbyl dihalides.

8. A composition according to claim 7, wherein the hydrocarbyl polyamineis of the general formula:

wherein:

a is in the range of 1 to c is in the range of l to 4 and equal to orless than the number of nitrogen atoms; and R is a branched chainaliphatic hydrocarbyl group derived from olefins of from three to fourcarbon atoms and of an average molecular weight in the range from about560 to about 2,000. 9. A composition according to claim 8, wherein the 5hydrocarbyl polyamine is a polyisobutenyl ethylene diamine having fromone to two polyisobutenyl groups of from about 560 to about 2,000average molecular weight.

10. A composition according to claim 8, wherein the hydrocarbylpolyamine is a polyisobutenyl diethylenetriamine having from one to twopolyisobutenyl groups of from about 560 to about 2,000 average molecularweight.

11. A composition according to claim 8, wherein the hydrocarbyl polamineis a polyisobutenyl triethylenetetramine having from one to threepolyisobutenyl triethylenetetramine having from one to threepolyisobutenyl groups of from about 560 to about 2,000 average molecularweight.

12. A composition according to claim 8, wherein the hydrocarbylpolyamine is a polyisobutenyl tetraethylenepentamine having from one tothree polyisobutenyl groups of from about 560 to about 2,000 averagemolecular weight.

13. A composition according to claim 7, wherein the coupling agent isdichlorobutene.

14; A composition according to claim 7, wherein the coupling agent isterephthaloyl chloride.

15. A composition according to claim 7, wherein the coupling agent isp-bis(chloromethyl)benzene.

16. A composition according to claim 7, wherein the coupling agent istoluene diisocyanate.

Po-ww UNITED STATES PATENT 0mm CERTIFICATE OF COREC'HUN Patent No. 75789 Y Dated January 15, 1974 LEWIS R. HONNEN and MARVIN D. COONInventor(s) I It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

F Column ll, line 28, the formula should read:

{groups Column 12, lines 16 20, should read:

--having from one to three polyisobutenyl molecular weight.

I Signed and sealed this 5th day of November 1974.,

(SEAL) Attest:

C. MARSHALL DANN Commissioner of Patents McCOY M. GIBSON JR. AttestingOfficer

2. A composition according to claim 1, wherein the hydrocarbyl polyamineis of the general formula:
 3. A composition according to claim 2,wherein the hydrocarbyl polyamine is a polyisobutenyl ethylene diaminehaving from one to two polyisobutenyl groups of from about 560 to about2,000 average molecular weight.
 4. A composition according to claim 2,wherein the hydrocarbyl polyamIne is a polyisobutenyl diethylenetriaminehaving from one to two polyisobutenyl groups of from about 560 to about2,000 average molecular weight.
 5. A composition according to claim 2,wherein the hydrocarbyl polyamine is a polyisobutenyltriethylenetetramine having from one to three polyisobutenyl groups offrom about 560 to about 2, 000 average molecular weight.
 6. Acomposition according to claim 2, wherein the hydrocarbyl polyamine is apolyisobutenyl tetraethylenepentamine having from 1 to 3 isobutenylgroups of from about 560 to about 2,000 average molecular weight.
 7. Afuel composition having a major amount of a hydrocarbonaceous liquidfuel and in an amount to provide detergency, the reaction product of ahydrocarbyl amine wherein the hydrocarbyl is of from 40 to 300 carbonatoms and is an aliphatic or alicyclic branched chain hydrocarbylradical derived from petroleum hydrocarbons or polyolefins of monomersfrom two to six carbon atoms, with the proviso that when the monomer isethylene, it is copolymerized with a higher homolog; and a couplingagent selected from the group consisting of C2-C20 polycarboxylic acids,C8-C20 polyisocyanates having a molecular weight below 400 and C2-C20hydrocarbyl dihalides.
 8. A composition according to claim 7, whereinthe hydrocarbyl polyamine is of the general formula: (-N(-CH2CH2N-)a)R1c H3 a c wherein: a1 is in the range of 1 to 5; c1 is in the range of1 to 4 and equal to or less than the number of nitrogen atoms; and R1 isa branched chain aliphatic hydrocarbyl group derived from olefins offrom three to four carbon atoms and of an average molecular weight inthe range from about 560 to about 2,000.
 9. A composition according toclaim 8, wherein the hydrocarbyl polyamine is a polyisobutenyl ethylenediamine having from one to two polyisobutenyl groups of from about 560to about 2,000 average molecular weight.
 10. A composition according toclaim 8, wherein the hydrocarbyl polyamine is a polyisobutenyldiethylenetriamine having from one to two polyisobutenyl groups of fromabout 560 to about 2,000 average molecular weight.
 11. A compositionaccording to claim 8, wherein the hydrocarbyl polamine is apolyisobutenyl triethylenetetramine having from one to threepolyisobutenyl triethylenetetramine having from one to threepolyisobutenyl groups of from about 560 to about 2,000 average molecularweight.
 12. A composition according to claim 8, wherein the hydrocarbylpolyamine is a polyisobutenyl tetraethylenepentamine having from one tothree polyisobutenyl groups of from about 560 to about 2, 000 averagemolecular weight.
 13. A composition according to claim 7, wherein thecoupling agent is dichlorobutene.
 14. A composition according to claim7, wherein the coupling agent is terephthaloyl chloride.
 15. Acomposition according to claim 7, wherein the coupling agent isp-bis(chloromethyl)benzene.
 16. A composition according to claim 7,wherein the coupling agent is toluene diisocyanate.